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Cited by 171Advanced NMR Techniques and ApplicationsElectron Spin Resonance StudiesMagnetism in coordination complexes

Computationally Assisted Design of Polarizing Agents for Dynamic Nuclear Polarization Enhanced NMR: The AsymPol Family

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Mentink-Vigier, Frédéric, Marin-Montesinos, Ildefonso, Jagtap, Anil P., Halbritter, Thomas, van Tol, Johan, Hediger, Sabine, Lee, Daniel, Sigurdsson, Snorri Th. +1 more·2018·Journal of the American Chemical Society
DOI 10.1021/jacs.8b04911PMC PMC6145599
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Abstract

We introduce a new family of highly efficient polarizing agents for dynamic nuclear polarization (DNP)-enhanced nuclear magnetic resonance (NMR) applications, composed of asymmetric bis-nitroxides, in which a piperidine-based radical and a pyrrolinoxyl or a proxyl radical are linked together. The design of the AsymPol family was guided by the use of advanced simulations that allow computation of the impact of the radical structure on DNP efficiency. These simulations suggested the use of a relatively short linker with the intention to generate a sizable intramolecular electron dipolar coupling/J-exchange interaction, while avoiding parallel nitroxide orientations. The characteristics of AsymPol were further tuned, for instance with the addition of a conjugated carbon–carbon double bond in the 5-membered ring to improve the rigidity and provide a favorable relative orientation, the replacement of methyls by spirocyclohexanolyl groups to slow the electron spin relaxation, and the introduction of phosphate groups to yield highly water-soluble dopants. An in-depth experimental and theoretical study for two members of the family, AsymPol and AsymPolPOK, is presented here. We report substantial sensitivity gains at both 9.4 and 18.8 T. The robust efficiency of this new family is further demonstrated through high-resolution surface characterization of an important industrial catalyst using fast sample spinning at 18.8 T. This work highlights a new direction for polarizing agent design and the critical importance of computations in this process.

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  • Introducing the biradical AsymPolPOK into intact cells achieved a 57-fold enhancement in NMR sensitivity for carbohydrates, which reduced measurement time by 3,249-fold.

    “To investigate whether caspofungin treatment affects the spatial organization of polysaccharides within the mechanical core of C. auris cell wall, we introduced the biradical AsymPolPOK83 into intact cells, achieving a 57-fold enhancement in the NMR sensitivity for carbohydrates (Fig. 5a), which reduced measurement time by 3,249-fold.”

    From Distinct echinocandin responses of Candida albicans and Candida auris cell walls revealed by solid-state NMR (2025) · cites this paper as [83]

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Cited by

Sorted by citations

Authors
Mentink-Vigier, F., Marin-Montesinos, I., Jagtap, A. P., Halbritter, T., van Tol, J., Hediger, S., Lee, D., Sigurdsson, S. T., & De Paëpe, G.
Affiliations
  • Univ. Grenoble Alpes, CEA, CNRS, INAC-MEM , ,
  • University of Iceland (IS)
  • EMR National High Magnetic Field Laboratory , 1800 E. Paul Dirac Drive , , ,
  • Centre National de la Recherche Scientifique (FR)
ORCID
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2018-08-10
Volume
140
Issue
35
Pages
11013-11019
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/jacs.8b04911
PMC
PMC6145599
OpenAlex
W2885099057
Cited by
171
References
0
Citations by year
2026: 15 · 2025: 28 · 2024: 28 · 2023: 20 · 2022: 25 · 2021: 21 · 2020: 20 · 2019: 13 · 2017: 1
FWCI
5.83
Type
journal article
Language
en
Open access
Licence
Locations
  • Journal of the American Chemical Society (publishedVersion, other-oa)
  • Europe PMC (PubMed Central) (publishedVersion)
  • PubMed Central (publishedVersion)
  • PubMed (publishedVersion)
  • HAL (submittedVersion, other-oa)
  • Research Explorer (The University of Manchester) (submittedVersion)
Funders
  • H2020 European Research Council (682895)
  • Agence Nationale de la Recherche (ANR-11-LABX-0003-01, ANR-12-BS08-0016-01)
  • Rannsóknasjóður (141062-051)
Topics
  • Physical Sciences › Chemistry › Spectroscopy › Advanced NMR Techniques and Applications
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Biophysics › Electron Spin Resonance Studies
  • Physical Sciences › Materials Science › Electronic, Optical and Magnetic Materials › Magnetism in coordination complexes
Keywords
dynamic nuclear polarization, polarizing agents, electron spin relaxation, NMR sensitivity enhancement, catalyst surface characterization
MeSH terms
Magnetic Resonance Spectroscopy, Organic Chemicals, Molecular Structure, Computer-Aided Design

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